Leuco-alkali preparations of sulfur dyestuffs and process of making same.



ALBRECHT SCHMIDT AND ADOLF STEINDORFF, (ll? HQCPIST-ON-THE-MAIN,GERMANY,

ASSIGNORS T0 FABBWERKE VORM. MEXSTER LUQIUS dc BRUNING, OE H'jCHST-ON-THE-MAIN, GERMANY, A CORPQRATION 01? GER-MANY.

LEUCU-ALILALI PR-EPARATIQNS 03E SULFUR lTiY'ESTUFFS AND PROCESS OFMAKING SAME.

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No Brewing.

To all whom "it away cont-em:

Be it known that we, ALBuncirr SCHMIDT, l h. D., chemist, and AcoiirSTEINDOHFF, Ph. 1)., chemist, citizens of the Empire of Germany,residing at Hochst-on-the-Main, Germany, have invented certain new anduseful improvements in lQeuco-Allrali Preparations of Sulfur llyestui'lsand Processes of Makdescribed we have found that by proceeding inanother Way much more valuable and stable products can be obtained,namely products of leuco-alkali salts, by completely reducing the sulfurdyestuffs to the lowest leuco degree With alkaline reducing agents inpresence of alkalis, such agents being for instance. glucose. andalkali-with or without an excess of glucoseor a'inixture of. glib coseand hydrosulfite, and then evaporating the solution to dryness,preferably in cacao, advantageously without isolating theleucocompoi'uid from the solution. There are thus obtained frothy orgranulated products in a form which is Well adapted. for commercial use,very stable, ver r readily soluble and capable of dyeing even in the socalled cold lime-fermentation vat and cold lime-glucose vat.

i'iccording to the new process, the sulfur dyestuils are advantageouslyused in the form of pastes free from sulfur and sodium suliid. Thus theprocedure may, for instance, be as follows: The sulfur dyestuil is firstboiled or heated with an alkaline solution oi? glucose and then it isevaporated or boiled down to dryness preterably in a vacudnr-with orwithout the addition of further reducing-agent, such as liydrosulfite,glucose etc. By alkaline reducing agents are to be understood in thepresent application, such reducing agents (except the alkali sulfide) asare capable of reducing in presence of an alkali, the most appropriateSpecification of Letters Patent.

Patented iilay 5, 191a.

Application filed February 2?, 1912 Serial Nol 680,835.

substances being glucose and its technical equivalents, such forinstance, as maltose, levulose, wood-molasses or the like, or mixturesof, for instance, about equal parts of glucose, etc, and Wood molasses,said substances to be comprised under the term glucose-like products.

The above-described process possesses new and surprising features inseveral respects: F or instance the preparations of alkaline leuco thusproduced aredistinguished from the products obtained by a mixture withcarbohydrates according to German .Patent No. 200,?91, in that theformer are capable of dyeing good and intense tints evenin the coldglucose lime vat and in the cold lime-fermentation vat (both these andsiinilarvats beii'ig comprised under theter n .cold lime-vats); whereasthe other products (obtained by a mixture with carbohydrates) yield inthe said vats only very weak tints; indeed they only dye in the coldsodiuiuglucose-vat, and in this case the tints are much weaker thanthose obtainable by the present new process. Furthermore, on comparingthe vat liquors prepared from the two kinds of products, they are foundto be of quite a difierent pearance, showing, according to the presentprocess, quite a different state of reduction and solubility, etc, bothdirectly on the set-- ting of the vat and when it is further worked Theobtained from the preparations of the present application may also beworked simply with a small quantity of glucose or its equivalents andliine,.without hydrogen fermentation, or the addition of a substanceproducing such fermen ation, be-

ins; required The products obtained accordiugto the present applicationare also entirely oistinguished by their said behavior in the coldglucose-lineor cold lime fermentation vat, from. the products derivedironi sulfur dyestuils treat d with glucdse as described in GermanPatent No.

198,691, and which are not obtained by mixing suliur dyestuffs withcarbohydrates (as described in German Patent No. 200,391) but by heatingthe sulfur dyestuil's with a glucose solution in absence of alkalil -According to the present application there are used and evaporated todryness, just those leuco alkalisalt solutions which tare statedinGerman Patent No. 198,691 to be unsuitable for the purpose in questionfor several reasons, for instance for the reason that the reduction byn'ieans of glucose and alkalil'iydratc proceeded too tar. Therefore itcould not. at all be foreseen that, by further evaporation and dryii'igof these alkaline leuco-salt solutions, either with or without. aneXcess of the reducing! agent, it was possible by the present])1'0C(..,:-1 to obtain, without destroying the molecule of the sulfurdycstutl', }'Jl' "l)t1;lll\')l"" "essing the very valuable new techni lproperty of dyeing in the lime val, that is to say of yielding leuco('Hil'll'llllilllli :uipuri-ntly so far reduced that; their lime saltsare soluble. Furthermore it is a most surprising lact. that. the dryalkaline -l( lt'()-S5tlt preparations thus produced are oi excellentstability, not to mention the other technical advantages they possess.

[Cw rimples.

(l) 100 kg. thiogene black M paste of 20 per cent. strength are heatedfor some time to boiling with kg. of caustic soda lye of B. and 10 kg.of glucose; this mixture is rapidly evaporated to dry ness in a vacuum,after adding, it required, 3 kg. of hydrosulfite powder. The resultingporous product, which has a black luster, dissolves in water so as toform a green vat which can immediately be used for black dyeings, afteradding, it required some alkali and a small quantity ofhydrosulfitepowder, or glucose, or after supplying it with lime orpotash, or sodium carbonate and glucose. or any other organic reducingagents, The product: thus obtained, which is free or almost. free fromglucose, is 0 excellent stability. When using larger quantitles ofglucose thei are also obtained stable products which, during the workingof the vat, require no, or only a small, fu ther quantity glucose.

' 400 kg. of thio rcne green G. G. cone. powder are heaved :tor ashorttime with 800 liters of water, 200 kg. of glucose and 600 l. of causticsoda lye of 40 B., and after having added about kg. of hydrosullitepowder the mass evaporated to dryness in a vacuum. The brownish-blackfriabl product can be immediately used for dyeiug grreen tints.

(3) 100 kg. of: thiogene new blue QRL, 1n the form of a paste of 20%strength, are heated with 30 he. of caustic soda lye of 40 B63, and ii)kg. ol. glucose and, after laving added 3 kg. of liydrosulfite powder,the mass is evaporated. The product which has a dark-brown luster,yields a reddish vat which on addition of some mill; of lime turnssomewhat yellowish. This vat an be used directly for dyeing. The dyeingsobtainable by means of this preparation, for instance the blue tintsobtained from thiogene deep blue. are remarkable for their intense redhue. Similar piwparations, also readily soluble and dyeing: directlyeven in the lime vat, can be obtained from the other sulfur dyestull's.for instance from the thiogene yellows, the sulfur yellow G. cxti'a,thiogcne brown (r R. coma, thiogenc cyanin, and their more highlysulfurizcd dcrivatives which are more dillirullly soluble in sodiumsultid, such as are obtained when using highly sult'urized polysullids.

l) 20 kg. of thiogcne green i. L. extra conc. powder or any other ihie'cnc-dyestufl', such as tl1io;rcne-blue, thion'ouc-black,.thiogone-brown, thiogcne-ycllow, chm, are heated with about 3 kg. ofwood molasses (sulfite-cellulose-pitch) dissolved. in liters of water,and with 110 k of. caustic soda lye of 40 136., and, after having; added2 kn. of hydrosulfite powder or glucose or'the like. the mass is eaporatcd to dryness. The dark, frothy product is readily soluble in thelime vat; the vat, which shows a brown color, can be directly used fordyciin Having now described our invention,

what we claim is:

1. The process of manutaoturin; new solid and stable leuco-alkahprermrations of sulfur-dyestuffs, which consists in cvapo at- 'ingsulfur dyestuffs to dLynQss with glu- ALBRECHT SCHMIDT. ADOLFSTETNDORFF.

Witnesses 2 JEAN GRUM), CARL GRUNI).

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3 It is hereby certified that in Lettere Patent No. 1,095,237, grantedMay 5, 1914-,

upon the epplication of Albrecht Schmidt end Adolf Steindorfi, ofHochst-on-the- Main, Germany, for an improvement in lJeueo-AlkztliPreparations of Sulfur Dyestutl's and Processes of Making Same, an errorappezlrs in the printed specification: i'equlring correction as follows:Page 1, line 95, for the compound W01Cl glucoseline read glztcoselz'me;and that the said Letters Patent should be read with this oor 'eotiontherein that the seine lgley conform to the l'e col 'd of the case inthe Patent Office. I

Signed and sealed this 6th day of July, 1)., 1915.

[SEAL] R. F. WHITEHEAD,

Correction in Letters Patent No l,095,237

Acting Commissioner of Paients

